Substituted benzotriazole phenolate salts and antioxidant compositions formed therefrom

ABSTRACT

A class of antioxidant compositions include benzotriazole phenolate salts with substituents either ortho to the phenol hydroxide group and/or para to the phenol hydroxide group can be prepared from substituted benzotriazole phenols. The ortho substituent group can be a simple hydrocarbon, alkoxy or amino group, or the ortho substituent group can be a linking group, linking the benzotriazole phenolate to another benzotriazole phenolate group.

FIELD OF THE DISCLOSURE

This disclosure relates to substituted benzotriazole phenolate salts andantioxidant compositions formed from them.

BACKGROUND

Phenols are a class of chemical compounds having a hydroxyl groupdirectly bonded to an aromatic hydrocarbon group. Phenolates are theanionic salts of phenols in which a proton has been removed from thehydroxyl group of the phenol. A wide variety of phenolics, as compoundsthat contain a phenol group are called, are known. Some phenolics areproduced by plants in nature and others have been synthetically designedfor a variety of chemical uses.

One class of phenolics are 2-(2-hydroxyphenyl)benzotriazoles orbenzotriazole phenols. Benzotriazole phenols are an important class ofUV absorbers, and in some cases, can absorb in the visible range aswell. These compounds are often used as additives in materials and caneven be incorporated into the polymeric structures via a polymerizablesubstituent on the benzotriazole phenol structure.

In addition to the usefulness of the benzotriazole phenols themselves,the benzotriazole phenols can also be used as synthons to formbenzotriazole phenolate salts that are also useful. For example in EPPatent Publication No. 351,732, the use of a variety of benzotriazolephenolate salts are used as the essential ingredient to give highcrystallization rates in polyester polymer compositions.

The need remains for substituted benzotriazole phenolate salts.

SUMMARY

Disclosed herein are substituted benzotriazole phenolate salts, andantioxidant compositions comprising these substituted benzotriazolephenolate salts. In some embodiments, the antioxidant compositioncomprises one or more macromolecular salt compositions, themacromolecular salt composition comprising an assembly of metal saltscomprising repeat units of a substituted benzotriazole phenolate anionand a metal cation with the structure:

where each R¹, R², R³, R⁴, R⁵, R⁶, R⁷, and R⁸, independently comprises ahydrogen atom, an alkyl group, an alkenyl group, an aryl group, ahalogen atom, or a substituted heteroatom group comprising a—B(OR¹⁸)(OR¹⁹), a —SiR²⁰ ₃, a —CH₂—R⁹, an —O—R⁹, a —N—R⁹R¹⁰, a —S—R⁹, a—S(O)—R⁹, or a —S(O)₂—R⁹ group, where S(O) is a sulfinyl group S═O, andS(O)₂ is a sulfonyl group O═S═O, R⁹ comprises a hydrogen atom, an alkylgroup, an alkenyl group, an aryl group, or a heteroatom-containing groupcomprising one or more oxygen, nitrogen, sulfur, or phosphorous atoms,wherein the —B(OR¹⁸)(OR¹⁹), —SiR²⁰ ₃, —CH₂—R⁹, —O—R⁹, —N—R⁹R¹⁰, —S—R⁹,—S(O)—R⁹, or —S(O)₂—R⁹ group may be neutral or anionic, and R¹⁰comprises a hydrogen atom, an alkyl group, an alkenyl group, an arylgroup, or a heteroatom-containing group comprising one or more oxygen,nitrogen, sulfur, or phosphorous atoms, or R⁹ and R¹⁰ together with theatoms connecting form a heterocyclic ring structure, R¹⁸ and R¹⁹ areindependently hydrogen atoms, alkyl groups or R¹⁸ and R¹⁹ together withthe atoms connecting form a heterocyclic ring structure, each R²⁰independently comprises an alkyl group; n is an integer of 1-4; and Mcomprises a metal atom with a valency of n; and the macromolecularassembly comprises 2-4 repeat units.

In other embodiments, the repeat unit of the macromolecular salt has thestructure:

where X comprises a —CH₂—, —O—, —S—, —S(O)—, —S(O)₂—, or —NR¹⁰— linkinggroup where R¹ comprises a hydrogen atom, an alkyl group, or an arylgroup, each R², R³, R⁴, R⁵, R⁶, R⁷, R⁸, R¹¹, R¹², R¹³, R¹⁴, R¹⁵, R¹⁶,and R¹⁷, independently comprises a hydrogen atom, an alkyl group, analkenyl group, an aryl group, or a halogen atom; m=0.5, 1, or 2; M is ametal ion with a valency of 2 m such that M is lithium sodium orpotassium when m=0.5; M is calcium, magnesium, or cobalt, when m=1; andM is vanadium or titanium when m=2.

BRIEF DESCRIPTION OF THE DRAWINGS

The present application may be more completely understood inconsideration of the following detailed description of variousembodiments of the disclosure in connection with the accompanyingdrawings.

FIG. 1 shows a view of NMR data for a precursor and for an embodiment ofan article of this disclosure.

DETAILED DESCRIPTION

One class of useful phenolics are 2-(2-hydroxyphenyl)benzotriazoles orbenzotriazole phenols. Benzotriazole phenols are an important class ofUV absorbers, and in some cases, can absorb in the visible range aswell. These compounds are often used as additives in materials,particularly polymeric materials, and can be used as synthons to preparebenzotriazole phenolate salts, which can also be useful as additives inmaterials, especially polymeric materials.

Phenols such as benzotriazole phenols are known to be absorbers oflight, especially UV (ultraviolet) light, but also in some instancesvisible light. A number of benzotriazole phenols are commerciallyavailable as light stabilizers, that is to say for incorporation intopolymeric matrices to protect the matrices from damage by UV light.

Disclosed herein are substituted benzotriazole phenolate salts whichhave a wide variety of desirable properties. The substitutedbenzotriazole phenolate salts have antioxidant properties. That is tosay that incorporation of the phenolate salts into polymeric matricesprotects that matrices from oxidation. This is very different from thelight stabilization properties of the phenols. This antioxidant propertycan be measured in a variety of ways as will be described in greaterdetail in the Examples section below. The ability of these salts toprovide protection from oxidation is a very useful property, as well asone that is not expected for this class of materials.

In addition, the substituted benzotriazole phenolate salts also have theunexpected property of fluorescence. Fluorescence is a well understoodproperty in which the material absorbs electromagnetic radiation of onewavelength and emits electromagnetic radiation of different, typicallylonger, wavelength. In the present disclosure, the substitutedbenzotriazole phenolate salts absorb light of UV wavelengths and emitslight in the visible range of wavelengths. This property has a widerange of uses, particularly when the fluorescent material is dispersedwithin a polymeric matrix. For example, a wide variety of safety andsecurity items utilize this property from signs and other safetyarticles where the fluorescence enhances the visibility of the safetyarticles, to security articles which can use the fluorescence forverification (the presence of fluorescence in a security document allowsfor verification of the authenticity of the security document byexposure to UV light and observation of the fluorescence). Thefluorescence of the substituted benzotriazole phenolate salts issurprising in view of the fact that the phenols from which the salts areprepared are not fluorescent.

Another property of these substituted benzotriazole phenolate salts istheir usefulness as charge enhancing additives for electret materials.This property is more fully disclosed in the application 62/189,515filed on the same day as the present application.

The substituted benzotriazole phenolate salts of this disclosure are notsimple salts of the type [anion][cation] such as one would expect forthis type of salt. Rather, the salts are macromolecular saltcompositions comprising an assembly of metal salts having repeat unitsof a substituted benzotriazole phenolate anion and metal cation(s) withthe general structure: {[anion][cation]}_(a) where a is an integer offrom two to four. The methods in which this macromolecular compositionhas been verified will be described in greater detail in the Examplessection. Nuclear magnetic resonance (NMR) spectra verifies that themacromolecular structure is present in solution.

The terms “a”, “an”, and “the” are used interchangeably with “at leastone” to mean one or more of the elements being described.

The term “alkyl” refers to a monovalent group that is a radical of analkane, which is a saturated hydrocarbon. The alkyl can be linear,branched, cyclic, or combinations thereof and typically has 1 to 20carbon atoms. In some embodiments, the alkyl group contains 1 to 18, 1to 12, 1 to 10, 1 to 8, 1 to 6, or 1 to 4 carbon atoms. Examples ofalkyl groups include, but are not limited to, methyl, ethyl, n-propyl,isopropyl, n-butyl, isobutyl, tert-butyl (t-butyl), n-pentyl, n-hexyl,cyclohexyl, n-heptyl, n-octyl, and ethylhexyl.

The term “alkenyl” refers to a monovalent group that is a radical of analkene, which is a hydrocarbon with at least one carbon-carbon doublebond. The alkenyl can be linear, branched, cyclic, or combinationsthereof and typically contains 2 to 20 carbon atoms. In someembodiments, the alkenyl contains 2 to 18, 2 to 12, 2 to 10, 4 to 10, 4to 8, 2 to 8, 2 to 6, or 2 to 4 carbon atoms. Exemplary alkenyl groupsinclude ethenyl, n-propenyl, and n-butenyl.

The term “alkaryl” as used herein refers to aryl substituted alkyl groupof the general structure —R^(a)—Ar, where R^(a) is an alkylene group andAr is an aryl group. An example of an alkaryl group is a benzyl group—CH₂-Ph.

The term “heteroatom substituted” refers to an alkyl, aryl or othergroup which contains heteroatoms. These heteroatoms may be pendantatoms, for example, halogens such as fluorine, chlorine, bromine, oriodine or catenary atoms such as nitrogen, oxygen, boron, or sulfur.

The term “alkoxy” refers to a group with the general structure —O—R,where R is an alkyl group. The term “aryloxy” refers to a group with thegeneral structure —O—R, where R is an aryl group. In some instances, theterm alkoxy is used generically to describe both alkoxy and aryloxygroups.

The term “aryl” refers to an aromatic carbocyclic group that is aradical containing 1 to 5 rings which may be connected or fused. Thearyl group may be substituted with alkyl or heteroalkyl groups. Examplesof aryl groups include phenyl groups, naphthalene groups and anthracenegroups.

The terms “room temperature” and “ambient temperature” are usedinterchangeably to mean temperatures in the range of 20° C. to 25° C.

Unless otherwise indicated, all numbers expressing feature sizes,amounts, and physical properties used in the specification and claimsare to be understood as being modified in all instances by the term“about.” Accordingly, unless indicated to the contrary, the numbers setforth are approximations that can vary depending upon the desiredproperties using the teachings disclosed herein.

Disclosed herein are compositions of matter comprising salts ofsubstituted benzotriazole phenolate anions and metal cations that aremacromolecular salts, and antioxidant compositions comprising one ormore macromolecular salts of substituted benzotriazole phenols.

Among the compositions disclosed herein are compositions of mattercomprising macromolecular salts of a substituted benzotriazole phenolateanion and a metal cation with repeating units with the structure ofFormula I:

In Formula I, at least one of R¹ and R³ comprises a substituent group,that is to say a group other than a hydrogen atom. In many embodiments,both R¹ and R³ comprise substituent groups. In some embodiments R¹ isnot substituted i.e. R¹ comprises a hydrogen atom, in many otherembodiments R¹ is a substituent group or another linked benzotriazolephenol group, as will be described in greater detail below.

In embodiments where R¹ is not substituted (i.e. is a hydrogen atom), R³comprises an alkyl, alkoxy or aryloxy group comprising 1-20 carbonatoms, and each R², R⁴, R⁵, R⁶, R⁷, and R⁸, independently comprises ahydrogen atom, an alkyl group, an alkenyl group, an aryl group, or ahalogen atom. In one embodiment, R¹ comprises a hydrogen atom, R³comprises an alkyl group with one carbon atom, and each R², R⁴, R⁵, R⁶,R⁷, and R⁸, independently comprises a hydrogen atom. In anotherembodiment, R¹ comprises a hydrogen atom, R³ comprises an alkoxy groupcomprising 4 carbon atoms, and each R², R⁴, R⁵, R⁶, R⁷, and R⁸,independently comprises a hydrogen atom.

In a wide variety of embodiments R¹ comprises a substituent group. Inthese embodiments, R¹ comprises a halogen atom, an alkyl or substitutedalkyl group, an alkenyl group, or a group comprising an —O—R⁹, a—N—R⁹R¹⁰, a —B(OR¹⁸)(OR¹⁹), or a —SiR²⁰ ₃. In these embodiments R⁹comprises a hydrogen atom, an alkyl group, an alkenyl group, an arylgroup, or a heteroatom-containing group comprising one or more oxygen,nitrogen, sulfur, or phosphorous atoms, and R¹⁰ comprises a hydrogenatom, an alkyl group, an alkenyl group, an aryl group, or aheteroatom-containing group comprising one or more oxygen, nitrogen,sulfur, or phosphorous atoms, or R⁹ and R¹⁰ together with the atomsconnecting form a heterocyclic ring structure, each R¹⁸ and R¹⁹ isindependently a hydrogen atom, an alkyl group, an aryl group, or R¹⁸ andR¹⁹ together with the atoms connecting form a heterocyclic ringstructure, each R²⁰ group is an alkyl group, and each R², R³, R⁴, R⁵,R⁶, R⁷, and R⁸, independently comprises a hydrogen atom, an alkyl group,an alkenyl group, an aryl group, or a halogen atom. Each of theseembodiments will be described in greater detail below.

In some embodiments, R¹ comprises a relatively small substituent group,one which is of smaller molecular weight and/or steric size relative tothe benzotriazole phenol base molecule. In other embodiments, the R¹group is a substituent group that is comparable in size and/or stericsize to the benzotriazole phenol base molecule, and is in fact anotherbenzotriazole phenol linked to the benzotriazole phenol base molecule byan oxygen-based, nitrogen-based, or carbon-based linking group. Examplesof the first type, where R¹ comprises a relatively small substituentgroup, will be presented first.

In some embodiments, R¹ comprises a halogen atom. Suitable halogen atomsinclude fluorine, bromine, chlorine and iodine. Bromine (Br) andchlorine (Cl) are particularly suitable.

In some embodiments, R¹ comprises an alkyl group, an alkenyl group, or asubstituted alkyl group. When R¹ comprises an alkyl group typically R¹comprises an alkyl group with 1-6 carbon atoms, in one particularembodiment R¹ comprises an alkyl group with 4 carbon atoms, generally atert-butyl group, and R³ is an alkyl group with 4 carbon atoms,typically a tert-butyl group. When R¹ comprises an alkenyl grouptypically R¹ comprises an alkenyl group with 1-6 carbon atoms, in oneparticular embodiment R¹ comprises an alkenyl group with 3 carbon atoms,generally a propenyl group, and R³ is an alkyl group with 1 carbon atom,typically a methyl group. When R¹ comprises a substituted alkyl grouptypically R¹ comprises an aryl substituted alkyl group with 1-12 carbonatoms, in one particular embodiment R¹ comprises an substituted alkylgroup with 10 carbon atoms, a 2,2-dimethyl-3-phenyl group, and R³ is analkyl group with 8 carbon atoms, typically an iso-octyl group.

In some embodiments, where R¹ comprises an —O—R⁹ group wherein R⁹comprises an alkyl group with 1-20 carbon atoms, or an aryl group. Inmany of these embodiments, R³ is also a substituent group, typically R³is an alkyl group with 1-20 carbon atoms.

In some embodiments, R⁹ comprises an alkyl group with 1-6 carbon atoms,in one particular embodiment R⁹ comprises an alkyl group with 4 carbonatoms, and R³ is an alkyl group with 8 carbon atoms, typically aniso-octyl group.

In other embodiments, R⁹ comprises an aryl group comprising asubstituted phenyl group. In some particular embodiments, R⁹ comprises a3-methyl phenyl group or a 4-methyl phenyl group, and R³ is an alkylgroup with 8 carbon atoms, typically an iso-octyl group.

In another group of embodiments, R¹ comprises an —N—R⁹R¹⁰ group. In someof these embodiments, R⁹ comprises an alkyl group with 1-20 carbonatoms, or an aryl group. In these embodiments, R¹⁰ independentlycomprises a hydrogen atom or alkyl group with 1-6 carbon atoms. In manyof these embodiments, R³ is also a substituent group, typically R³ is analkyl group with 1-20 carbon atoms.

In some embodiments, R⁹ comprises an alkyl group with 1-6 carbon atoms,or an aryl group comprising a 4-alkyl substituted phenyl group, whereinthe alkyl substituted group has 1-6 carbon atoms, and R¹⁰ comprises ahydrogen atom.

In one particular embodiment, R⁹ comprises an alkyl group with 1 carbonatom (a methyl group), R¹⁰ comprises a hydrogen atom, and R³ is an alkylgroup with 8 carbon atoms, typically an iso-octyl group. In oneparticular embodiment, R⁹ comprises an alkyl group with 6 carbon atoms,R¹⁰ comprises a hydrogen atom, and R³ is an alkyl group with 8 carbonatoms, typically an iso-octyl group. In yet another particularembodiment, R⁹ comprises a 4-alkyl substituted phenyl group, wherein thealkyl substituted group has 6 carbon atoms (i.e. the group comprises a4-hexyl phenyl group), R¹⁰ comprises a hydrogen atom, and R³ is an alkylgroup with 8 carbon atoms, typically an iso-octyl group.

In another particular embodiment, R¹ comprises a —B(OH)₂ group, in otherembodiments R¹ comprises —B(—O—C(Me)₂-C(Me)₂—O—), and R³ is an alkylgroup with 8 carbon atoms, typically an iso-octyl group.

In another particular embodiment, R¹ comprises a —SiR²⁰ ₃ group whereR²⁰ comprises an alkyl group with 1-6 carbon atoms, in some embodimentsR²⁰ comprises 3 carbon atoms, typically R²⁰ comprises an isopropylgroup.

In Formula I, M is a main group or transition metal ion with a valencyof n, and n also describes the stoichiometry of the anionic portion ofthe salt. Typically n is an integer of 1-4. If n is 1, the metal salt Mis a monovalent metal ion and the stoichiometry of the anionic portionis 1. If n is 2, the metal salt M is a divalent metal ion and thestoichiometry of the anionic portion is 2, meaning that two anions arepresent per M ion. Typically, the cationic portion of the macromolecularsalt, M, is a metallic cation with a valency of 1 or 2. In embodimentswhere M is monovalent, the M is lithium, sodium or potassium. Inembodiments where M is divalent, there are two equivalents of theanionic portion in the macromolecular salt, and M is calcium, magnesium,or cobalt. In some embodiments, M is a tetravalent metal ion (n=4) ortitanium or vanadium.

The salt shown in Formula I is a macromolecular salt, by which it ismeant that it is not a simple anion and cation combination, but is amore complex assembly of anions and cations. The salt shown in Formula Iis a repeat unit, and the salt comprises from 2 to 4 repeat units. Thestoichiometry of the salt (as defined by the value of n) is differentfrom the macromolecular nature of the salt. The stoichiometry merelyrefers to the charge balance of the salt, whereas the macromolecularnature of the salt refers to the presence of an extended assembly ofsalts. As was described above, a simple anion-cation salt would be ofthe type: [anion][cation], whereas the salts of this disclosure aremacromolecular salts of the type: {[anion][cation]}_(a), where a is aninteger of from 2 to 4.

As will be explained in greater detail in the Examples section, NMR(nuclear magnetic resonance) can be used to show that the salts aremacromolecular assemblies in solution. This NMR evidence is also shownin FIG. 1. To summarize, a characteristic alkyl group on the phenol fromwhich the salt is made shows a single peak. Upon formation of the salt,the single peak forms multiple peaks, demonstrating that thecharacteristic alkyl group is not a single peak as would be anticipatedfor a simple [anion][cation] salt. The presence of multiple peaks showsthat the characteristic alkyl group on the anion experiences slightlydifferent environments because the anions are part of the macromolecularassembly. Analysis of NMR Diffusion measurements can be used todetermine the number of repeat units in the macromolecular assembly (thevalue of a shown above), which is generally 2-4.

As mentioned above, in other embodiments the R¹ group is a substituentgroup that is comparable in size and/or steric size to the benzotriazolephenolate base molecule, and is in fact another benzotriazole phenolatelinked to the benzotriazole phenolate base molecule by an oxygen,nitrogen-based, carbon-based, or sulfur-based linking group. Examples ofthis second type of compound are described by Formula II below:

The structure of Formula II can be viewed as compound of Formula I wherethe R¹ group is an —X—R⁹ group an X is a linking group comprising an—O—, —NR¹⁰—, —S—, —S(O)—, —S(O)₂—, or —CH₂—, where S(O) is a sulfinylgroup S═O, S(O)₂ is a sulfonyl group O═S═O, and where R¹⁰ comprises ahydrogen atom, an alkyl group, or an aryl group. The R⁹ group in theseembodiments is another benzotriazole phenolate group, which may be thesame or different from the base benzotriazole phenolate group. In theseembodiments, each R², R³, R⁴, R⁵, R⁶, R⁷, R⁸, R¹¹, R¹², R¹³, R¹⁴, R¹⁵,R¹⁶, and R¹⁷, independently comprises a hydrogen atom, an alkyl group,an alkenyl group, an aryl group, or a halogen atom.

In Formula II, M is a metal ion with a valency of 2 m, and m alsodescribes the stoichiometry of the anionic portion of the salt. In thisinstance, m can be a non-integer number, selected from 0.5, 1.0, or 2.If m is 0.5, the metal salt M is monovalent metal (2 m=1) and thestoichiometry of the anionic portion is 0.5 (i.e. one half the anionicportion per M, or 2 M ions per 1 anionic portion). If m is 1, the metalsalt M is a divalent metal ion and the stoichiometry of the anionicportion is 1. If m is 2, the metal salt M is a tetravalent metal ion andthe stoichiometry of the anionic portion is 2, meaning that two anionsare present per M ion. Typically, the cationic portion of themacromolecular salt, M, is a metallic cation with a valency of 1 or 2.In embodiments where M is monovalent, the M is lithium, sodium orpotassium. In embodiments where M is divalent, M is calcium, magnesium,or cobalt. In some embodiments, M is a tetravalent metal ion (m=2) ortitanium or vanadium.

In some embodiments of the compounds of Formula II, X comprises an—NR¹⁰-linking group where R¹⁰ comprises a hydrogen atom, or an alkylgroup comprising 1-3 carbon atoms. Typically in these embodiments, theR³ and R¹⁶ groups are substituent groups, where R³ and R¹⁶ each comprisean alkyl group with 1-20 carbon atoms. Typically, each R², R⁴, R⁵, R⁶,R⁷, R⁸, R¹¹, R¹², R¹³, R¹⁴, R¹⁵, and R¹⁷, is a hydrogen atom.

In one particular embodiment, X comprises an —NR¹⁰— linking group whereR¹⁰ comprises a hydrogen atom, the R³ and R¹⁶ groups are alkyl groupswith 8 carbon atoms, typically iso-octyl groups, and each R², R⁴, R⁵,R⁶, R⁷, R⁸, R¹¹, R¹², R¹³, R¹⁴, R¹⁵, and R¹⁷, is a hydrogen atom.

In another particular embodiment, X comprises an —NR¹⁰— linking groupwhere R¹⁰ comprises an alkyl group with 1 carbon atom (a methyl group),the R³ and R¹⁶ groups are alkyl groups with 8 carbon atoms, typicallyiso-octyl groups, and each R², R⁴, R⁵, R⁶, R⁷, R⁸, R¹¹, R¹², R¹³, R¹⁴,R¹⁵, and R¹⁷, is a hydrogen atom.

In some embodiments of the compounds of Formula II, X comprises an —O—linking group. Typically in these embodiments, the R³ and R¹⁶ groups aresubstituent groups, where R³ and R¹⁶ each comprise an alkyl group with1-20 carbon atoms. Typically, each R², R⁴, R⁵, R⁶, R⁷, R⁸, R¹¹, R¹²,R¹³, R¹⁴, R¹⁵, and R¹⁷, is a hydrogen atom.

In one particular embodiment, X comprises an —O— linking group, the R³and R¹⁶ groups are alkyl groups with 8 carbon atoms, typically iso-octylgroups, and each R², R⁴, R⁵, R⁶, R⁷, R⁸, R¹¹, R¹², R¹³, R¹⁴, R¹⁵, andR¹⁷, is a hydrogen atom.

In some embodiments of the compounds of Formula II, X comprises a —S—linking group. Typically in these embodiments, the R³ and R¹⁶ groups aresubstituent groups, where R³ and R¹⁶ each comprise an alkyl group with1-20 carbon atoms. Typically, each R², R⁴, R⁵, R⁶, R⁷, R⁸, R¹¹, R¹²,R¹³, R¹⁴, R¹⁵, and R¹⁷, is a hydrogen atom.

In one particular embodiment, X comprises a —S— linking group, the R³and R¹⁶ groups are alkyl groups with 8 carbon atoms, typically iso-octylgroups, and each R², R⁴, R⁵, R⁶, R⁷, R⁸, R¹¹, R¹², R¹³, R¹⁴, R¹⁵, andR¹⁷, is a hydrogen atom.

In some embodiments, X comprises a methylene group —CH₂—. Typically inthese embodiments, the R³ and R¹⁶ groups are substituent groups, whereR³ and R¹⁶ each comprise an alkyl group with 1-20 carbon atoms.Typically, each R², R⁴, R⁵, R⁶, R⁷, R⁸, R¹¹, R¹², R¹³, R¹⁴, R¹⁵, andR¹⁷, is a hydrogen atom. In a particular embodiment, R³ and R¹⁶ eachcomprise an iso-octyl group. The phenol from which this salt is preparedis commercially available from BASF as TINUVIN 360.

The macromolecular nature of the salt compositions was unexpected andhas been shown to be present in solution. The methodology for confirmingthe macromolecular nature of these salts is described in greater detailin the Examples section below. While not wishing to be bound by theory,it is believed that the unexpected macromolecular structure of the saltcomposition also impacts the other unexpected properties of these salts,especially their anti-oxidant activity and their fluorescence.

Also disclosed are a new class of antioxidant compositions. Theseantioxidant compositions comprise at least one of the macromolecularsalts described above. These antioxidant compositions are useful in awide range of applications. Among these applications are the addition ofthese compositions to polymeric matrices. A wide range of matrices aresuitable as are described in application 62/189,493 filed on the sameday as the present application.

One particular application for which these salts, macromolecular salts,and antioxidant compositions have been shown to be particularly suitableis as charge additives in electret articles. This is described inapplication 62/189,515 filed on the same day as the present application.

Descriptions for the preparation of the substituted benzotriazolephenolate salts and the antioxidant compositions prepared from them aredescribed in detail below in the Examples section.

EXAMPLES

These examples are merely for illustrative purposes only and are notmeant to be limiting on the scope of the appended claims. All parts,percentages, ratios, etc. in the examples and the rest of thespecification are by weight, unless noted otherwise. Solvents were AlfaAesar (ChemSeal grade) and were used with no further purification.Solvents that were used in separations, isolations, chromatography, andother general use were obtained from EMD (Omnisolv Grade).

The following abbreviations are used throughout the Examples: M=molar;min=minutes; h=hours; equiv=equivalents; x=times; g=grams;mg=milligrams; mmol=millimoles; L=liters; mL=milliliters; rt=roomtemperature; aq=aqueous; RBF=round bottom flask.

Materials

The following is a table of commercially available materials andreagents that were used.

Compound Supplier Bases sodium ethoxide (ca. 20% in Ethanol) TCI Americasodium tert-butoxide TCI America n-butyllithium (1.6M in hexanes)Sigma-Aldrich potassium carbonate EMD Millipore cesium carbonate AlfaAesar potassium hydroxide EMD Millipore triethylamine Sigma-Aldrichsodium bicarbonate Sigma-Aldrich ammonium chloride VWR Oxidants1,3-Dibromo-5,5-dimethylhydantoin Alfa Aesar hydrogen peroxide, 30% J.T. Baker urea hydrogen peroxide adduct Alfa Aesar m-chloroperoxybenzoicacid Alfa Aesar Ligands 2-(Dicyclohexylphosphino)-2′,4′,6′-tri-i-propyl-Strem 1,1′-biphenyl (XPhos)2-(Di-t-butylphosphino)-3-methoxy-6-methyl-2′- Strem4′-6′-tri-i-propyl-1,1′-biphenyl (RockPhos)2-(Di-t-butylphosphino)-3,6-dimethoxy-2′,4′,6′-tri- Stremi-propyl-1,1′-biphenyl (t-buBrettPhos)1,1′bis(diphenylphospino)ferrocene Strem Catalyststris(dibenzylideneacetone)dipalladium Strem palladium acetate TCIAmerica allylpalladium(II) chloride dimer Lancaster copper acetate AlfaAesar Methanesulfonato(2-(di-t-butylphosphino)-3,6- Stremdimethoxy-2′,4′,6′-tri-i-propyl-1,1′-biphenyl)(2′-amino-1,1′-biphenyl-2-yl)palladium(II) (XPhos Precatalyst)Methanesulfonato(2-(di-t-butylphosphino)-3- Stremmethoxy-6-methyl-2′,4′,6′-tri-i-propyl-1,1′-biphenyl)(2′-amino-1,1′-biphenyl-2- yl)palladium(II) (RockPhosPrecatalyst) Methanesulfonato(2-(di-t-butylphosphino)-3,6- Stremdimethoxy-2′,4′,6′-tri-i-propyl-1,1′-biphenyl)(2′-amino-1,1′-biphenyl-2-yl)palladium(II) (t-BuBrettPhos Precatalyst)Reagents p-tolylboronic acid Aldrich Chemical trimethylborate Alfa Aesariodomethane Alfa Aesar triisopropylchlorosilane Alfa Aesar borontribromide Sigma-Aldrich thionyl chloride Alfa Aesartrifluoromethanesulfonic anhydride Oakwood2-(2H-Benzotriazol-2-yl)-4-(1,1,3,3- TCI America tetramethylbutyl)phenolm-cresol Alfa Aesar n-butanol Sigma-Aldrich methylamine hydrochlorideAldrich Chemical 4-n-hexylaniline Alfa Aesar hexylamine Alfa Aesarammonia (0.5M in dioxane) Sigma Aldrich scandium triflate Strem4-methylbenzenethiol toluene Alfa Aesar potassium thioacetate Alfa Aesar3,5-bis(trifluoromethyl)aniline Alfa Aesar1-bromo-4-(heptadecafluorooctyl)benzene Sigma Aldrich 1-iodooctadecaneAlfa Aesar

Structural Formulas of Phenol and Protected Phenol (Ether) CompoundsDisclosed

The table below presents a summary of the structural formulas for thephenol compounds used in this application to prepare phenolate salts.The phenols are either commercially available or prepared in theSynthesis Examples below.

TABLE A Listing of Phenol Structure Name Source Structure Ether-1Synthesis Example SE2

Phenol-1 Commercially available

Phenol-2 Commercially Available

Phenol-3 Synthesis Example SE1

Phenol-4 Commercially Available

Phenol-5 Synthesis Example SE2

Phenol-6 Synthesis Example SE3

Phenol-7 Synthesis Example SE4

Phenol-8 Synthesis Example SE5

Phenol-9 Synthesis Example SE6

Phenol-10 Commercially Available

Phenol-11 Synthesis Example SE7

Phenol-12 Commercially Available

Phenol-13 Synthesis Example SE8

Phenol-14 Synthesis Example SE9

Phenol-15 Synthesis Example SE10

Phenol-16 Commercially Available

Phenol-17 Synthesis Example SE11

Phenol-18 Synthesis Example SE12

Phenol-19 Synthesis Example SE13

Phenol-20 Synthesis Example SE14

Phenol-21 Synthesis Example SE15

Phenol-22 Synthesis Example SE16

Phenol-23 Synthesis Example SE17

Phenol-24 Synthesis Example SE18

General Synthesis of Phenols

In the examples below automated flash chromatography (AFC) was carriedout using an ISOLERA system available from Biotage, Inc,Charlottesville, Va., USA. For these purifications Biotage SNAP Ultrasilica columns were used with a hexane/ethyl acetate gradient mixture.

All intermediates and products were confirmed using ¹H and ¹³C NuclearMagnetic Resonance (NMR) on a 500 MHz Bruker instrument. In some casesHRMS was also obtained.

A specialized reaction was used to prepare Phenol-3 as shown inSynthesis Example SE1 below, for the other phenols synthesized, GeneralReaction Scheme I was followed.

Synthesis Example SE1: Phenol-3

The diazo compound above as synthesized following standard diazotizationprocedure (WO008131921; Bioorg. Med. Chem. Lett. 2010, 20, 4193-4195.),followed by reductive cyclization to give Phenol-3.

A General Reaction Scheme I is presented below which was followed toprepare the a number of phenols used to prepare the phenolate salts ofthis disclosure. Specific details are provided for each SynthesisExample.

Part A: Cross-Coupling. Protected phenol A is subjected tocross-coupling conditions with either a palladium or copper catalyst.For specific reaction conditions, see each individual example.

Palladium Catalysis (Buchwald-Hartwig Cross-Coupling):

Buchwald, Hartwig, and coworkers have reported in the literature atransformation in which aryl halides can be converted to heteroatoms byuse of a palladium catalyst and a bulky phosphine ligand. The followingcommercially available ligands (developed by Buchwald) have been used tosynthesize benzotriazole phenolic analogs in which a heteroatom has beenintroduced in the ortho position (see compound B). These ligands canalso be purchased already complexed to the palladium catalyst and arereferred to as precatalysts.

Copper Catalysis (Chan-Evans-Lam Coupling):

Copper can also be used to effect cross-coupling reactions betweenarylboronic acids and phenols, anilines, or arylthiols.

This is considered to be a modification of the Ullmann condensation, asdescribed in Kürti, L.; Czakó. Strategic Applications of Named Reactionsin Organic Synthesis, 1^(st) ed. Burlington: MA, 2005, pp. 464-465. Thereaction is stoichiometric in copper salts and is typically performedunder ambient conditions.

Part B: Deprotection of Methyl Ether. The methoxy ether benzotriazole(B, P=Me) was dissolved in dichloromethane (0.1 M) and cooled to −78° C.while stirring under N₂. Boron tribromide (1 equivalent per protectedphenol) was added dropwise and the reaction mixture allowed to slowlywarm to room temperature. When the reaction was complete (analysis byTLC), water was added dropwise and the mixture was stirred for 10 min.The organic layer was separated and the aqueous layer extracted with DCM(2×). The combined organic layers were washed with saturated aqueousNaHCO₃ and brine, dried (Na₂SO₄ or MgSO₄), filtered and concentrated.The residue was purified (SiO₂) to give products in 78-98% yield.

Note that in the following Synthesis Examples, compounds that arereferred to as “Ethers” are protected phenols, meaning that the —OHgroup is instead a “protected hydroxyl group” i.e. a —OCH₃ group, whichis deprotected to reform the phenolic hydroxyl group.

Synthesis Example SE2: Ether-1 and Phenol-52-(3-bromo-2-methoxy-5-(2,4,4-trimethylpentan-2-yl)phenyl)-2H-1,2,3-benzotriazole

Part A: Bromination.2-(2H-Benzotriazol-2-yl)-4-(1,1,3,3-tetramethylbutyl)phenol (100 g, 309mmol) was placed in a 1 L round bottom flask fitted with a stir bar anddissolved in chloroform (500 mL). To this was added1,3-dibromo-5,5-dimethylhydantoin (DBDMH) (45.95 g, 161 mmol) and themixture stirred rt overnight. After such time, the mixture was filteredand concentrated to give a dark red residue. The residue wasrecrystallized from dichloromethane/ethanol to obtain white crystals.Multiple recrystallizations of the mother liquor yielded 113 g of pureproduct (91% yield) of Phenol-5.

Part B: Methylation. The reaction product from Part A was placed in a 1L round bottom flask fitted with a stir bar and dissolved inacetonitrile (400 mL). Potassium carbonate (20.70 g, 150 mmol) was addedfollowed by iodomethane (3.3 mL, 52.5 mmol). The mixture stirred rtovernight. After such time, the reaction mixture was partiallyconcentrated, diluted with ethyl acetate and filtered over celite. Thesolution was concentrated, giving a thick beige oil, which eventuallysolidified over time to give 20.8 g (quantitative yield) of product ofEther 1.

Synthesis Example SE3: Phenol-62-(2H-1,2,3-benzotriazol-2-yl)-6-((triisopropylsilyl)oxy)-4-(2,4,4-trimethylpentan-2-yl)phenol

Part A. The reaction product from Synthesis Example SE2 was silylatedwith triisopropylchlorosilane (TIPS-Cl) following standard procedures.

Part B. The reaction product from Part A (1.57 g, 2.81 mmol) was placedinto a round bottom flask containing a stir bar and charged with N₂. THF(20 mL) was added and the flask cooled to −78° C. n-Butyl lithium (1.8mL, 2.81 mmol) was added and the mixture was allowed to slowly warm tort and stir for 3 h. After such time, the reaction was quenched withsaturated ammonium chloride and the product extracted with EtOAc (3×).

The combined organic layers were washed with brine, dried and filtered.The crude residue was purified by AFC to give a colorless solid (0.74 g,55% yield).

Synthesis Example SE4: Phenol-72-(2H-1,2,3-benzotriazol-2-yl)-6-butoxy-4-(2,4,4-trimethylpentan-2-yl)phenol

Into three flame dried 40-dram vials, each equipped with a stir bar andactivated 4 Å molecular sieves was placed Ether 1 prepared in SynthesisExample SE1, (4.179 g, 10.04 mmol), cesium carbonate (4.91 g, 15.06mmol), allylpalladium chloride dimer (18.4 mg, 0.5 mol %), and RockPhosligand (23.4 mg, 0.5 mol %). Each vial was fitted with a septa cap andevacuated and backfilled with N₂ (3×). Toluene (10 mL), followed byanhydrous n-butanol (1.8 mL, 20.08 mmol) was added to each vial. Thevials were placed on a ChemGlass reaction block and heated to 100° C.for 72 h. After such time, the reaction mixtures were combined, filteredover celite, and concentrated. The crude residue was purified via flashcolumn chromatography to give a pale yellow solid (9.80 g, 79% yield).Following Part B (General Reaction Scheme I), the free phenol wasisolated as a beige solid after purification by flash columnchromatography (8.50 g, 85% yield).

Synthesis Example SE5: Phenol-82-(2H-benzo[d][1,2,3]triazol-2-yl)-6-(hexylamino)-4-(2,4,4-trimethylpentan-2-yl)phenol

Into three flame dried vials equipped with a stir bar was placed Ether 1prepared in Synthesis Example SE1, (1.66 g, 4 mmol),tris(dibenzylideneacetone)dipalladium(0) (73.3 mg, 0.08 mmol), XPhosligand (95.3 mg, 0.2 mmol), sodium tert-butoxide (538 mg, 5.6 mmol), and1-hexylamine (0.74 mL, 5.6 mmol). The vial was fitted with a septa capand evacuated and backfilled with N₂. Dioxane (20 mL) was added and thereaction was heated to 130° C. for 16 h. After such time, the mixtureswere cooled to rt, combined, diluted with EtOAc and filtered overcelite. The residue was purified via AFC. A beige solid was isolated(3.88 g, 74% yield). Following Part B (General Reaction Scheme I), gavethe free phenol as a yellow solid (3.32, 88% yield).

Synthesis Example SE6: Phenol-92-(2H-1,2,3-benzotriazol-2-yl)-6-(m-tolyloxy)-4-(2,4,4-trimethylpentan-2-yl)phenol

Into two flame dried 40-dram vials, each equipped with a stir bar andactivated 4 Å mol sieves was placed Ether 1 prepared in SynthesisExample SE1, (4.16 g, 10 mmol), potassium phosphate (4.25 g, 20 mmol),palladium(II) acetate (45 mg, 2 mol %), and RockPhos ligand (93 mg, 2mol %). Each vial was fitted with a septa cap and evacuated andbackfilled with N₂ (3×). Toluene (10 mL), followed by m-cresol (1.3 mL,12 mmol) was added to each vial. The vials were placed on a ChemGlassreaction block and heated to 100° C. for 16 h. After such time, thereaction mixtures were combined, filtered over celite, and concentrated.The crude residue was purified via flash column chromatography to give abeige solid (7.07 g, 80% yield. Following Part B (General ReactionScheme I), the free phenol was isolated as a beige solid afterpurification by flash column chromatography (6.50 g, 98% yield).

Synthesis Example SE7: Phenol-112-(2H-benzo[d][1,2,3]triazol-2-yl)-6-((4-hexylphenyl)amino)-4-(2,4,4-trimethylpentan-2-yl)phenol

Into three flame dried vials equipped with a stir bar was placed Ether 1prepared in Synthesis Example SE1, (1.66 g, 4 mmol),tris(dibenzylideneacetone)dipalladium(0) (73.3 mg, 0.08 mmol), XPhosligand (95.3 mg, 0.2 mmol), sodium tert-butoxide (538 mg, 5.6 mmol), and4-hexylaniline (1 mL, 5.6 mmol). The vial was fitted with a septa capand evacuated and backfilled with N₂. Dioxane (20 mL) was added and thereaction was heated to 130° C. for 16 h. After such time, the mixtureswere cooled to rt, combined, diluted with EtOAc and filtered overcelite. The residue was purified via AFC. A beige solid was isolated(3.88 g, 74% yield). Following Part B (General Reaction Scheme I), gavethe free phenol as a yellow solid (4.67 g, 96% yield).

Synthesis Example SE8: Phenol-136,6′-azanediylbis(2-(2H-benzo[d][1,2,3]triazol-2-yl)-4-(2,4,4-trimethylpentan-2-yl)phenol)

Part A. To an oven-dried Schlenk flask fitted with a stir bar was added4 Å molecular sieves, sodium tert-butoxide (23.37 mmol, 2.25 g),Pd₂(dba)₃ (0.33 mmol, 306 mg), XPhos (0.83 mmol, 398 mg) and Ether 1prepared in Synthesis Example SE1, (16.69 mmol, 6.95 g). The flask wasthen evacuated and flushed with N₂ (3×) and ammonia in dioxane (0.5 M,100 mL) was added via cannula. The Schlenk flask was closed and heatedto 130° C. for 16 h. After such time, the reaction mixture was dilutedwith EtOAc, filtered, and concentrated. The crude oil was purified viaflash column chromatography to give a beige solid.

Part B. The product of Part A was dissolved in dichloromethane (150 mL)and cooled to −78° C. while stirring under N₂. Boron tribromide (17.10mmol, 1.6 mL) was added dropwise and the reaction mixture allowed toslowly warm to rt. When the reaction was complete (analysis by TLC),water was added dropwise and the mixture was stirred for 10 min. Theorganic layer was separated and the aqueous layer extracted with DCM(2×). The combined organic layers were washed with saturated aqueousNaHCO₃ and brine, dried (Na₂SO₄ or MgSO₄), filtered and concentrated.The residue was recrystallized from hot acetone to give a yellowcrystalline solid (3.38 g, 61% yield from Ether 1).

Synthesis Example SE9: Phenol-146,6′-(methylazanediyl)bis(2-(2H-benzo[d][1,2,3]triazol-2-yl)-4-(2,4,4-trimethylpentan-2-yl)phenol)

Part A. The reaction product from Synthesis Example SE6, Part A (12.79mmol, 8.8 g) was dissolved in dimethylformamide (120 mL) and to this,sodium hydride (14.07 mmol, 0.56 g) was added under a stream of N₂ atrt. The mixture was stirred 10 min and then iodomethane (14.07 mmol,0.88 mL) was added and stirring continued for another 2 h. The reactionwas quenched with saturated aq ammonium chloride and extracted withEtOAc (3×). The combined organic layers were washed with water and thenbrine, dried with Na₂SO₄, filtered and concentrated. No furtherpurification was performed.

Part B. The product of Part B was dissolved in dichloromethane (150 mL)and cooled to −78° C. while stirring under N₂. Boron tribromide (17.10mmol, 1.6 mL) was added dropwise and the reaction mixture allowed toslowly warm to rt. When the reaction was complete (analysis by TLC),water was added dropwise and the mixture was stirred for 10 min. Theorganic layer was separated and the aqueous layer extracted with DCM(2×). The combined organic layers were washed with saturated aqueousNaHCO₃ and brine, dried (Na₂SO₄ or MgSO₄), filtered and concentrated.The residue was recrystallized from hot acetone to give a yellowcrystalline solid (6.74 g, 60% yield from Ether 1).

Synthesis Example SE10: Phenol-156,6′-thiobis(2-(2H-benzo[d][1,2,3]triazol-2-yl)-4-(2,4,4-trimethylpentan-2-yl)phenol)

To a flame dried vial equipped with a stir bar was placed3-bromo-2-methoxy-5-(2,4,4-trimethylpentan-2-yl)phenyl)-2H-1,2,3-benzotriazole(0.416 g, 1 mmol), potassium thioacetate (0.057 g, 0.5 mmol),Tris(dibenzylideneacetone)dipalladium(0) (0.023 g, 0.025 mmol),1,1′-Bis(diphenylphosphino)ferrocene (0.028 g, 0.05 mmol) and potassiumphosphate (0.127 g, 0.6 mmol). The vial was then evacuated and flushedwith N₂ (3×) and toluene (0.5 mL) and acetone (0.25 mL) was added. Thereaction mixture was stirred for 72 h at 130° C. After such time, themixture was cooled, filtered, and purified by flash columnchromatography to obtain 5 as a white solid (0.240 g, 68% yield).Following the procedure from Example 10, Part B, the product wasobtained as a white solid (0.230 g, 99% yield).

Synthesis Example SE11: Phenol 172-(2H-benzotriazol-2-yl)-6-((3,5-bis(trifluoromethyl)phenyl)amino)-4-(2,4,4-trimethylpentan-2-yl)phenol

Into a 250 mL Schlenk flask equipped with a stir bar was placed Ether-1from SE2, (20.0 g, 48.03 mmol), tris(dibenzylideneacetone)dipalladium(0)(1.04 g, 1.14 mmol), XPhos ligand (1.35 g, 2.75 mmol), sodiumtert-butoxide (7.63 g, 79.4 mmol), and 3,5-bis(trifluoromethyl)aniline(8 mL, 51.36 mmol). The Schlenk flask evacuated and backfilled with N₂.Dioxane (200 mL) was added and the reaction was heated to 130° C. for 16h. After such time, the mixture was cooled to rt, diluted with EtOAc,filtered over celite and concentrated. The residue was purified via AFC.A brown solid was isolated (26.8 g, 98% yield). Following Part B(General Reaction Scheme I), gave the free phenol as a yellow solid(21.3 g, 82% yield).

Synthesis Example SE12: Phenol 182-(2H-triazol-2-yl)-6-((4-(perfluorooctyl)phenyl)amino)-4-(2,4,4-trimethylpentan-2-yl)phenol

Into two flame dried 40-dram vials, each equipped with a stir bar wasplaced the aniline side product(3-(2H-benzo[d][1,2,3]triazol-2-yl)-2-methoxy-5-(2,4,4-trimethylpentan-2-yl)aniline)from SE8, Part A (1.162 g, 3.30 mmol),1-bromo-4-(heptadecafluorooctyl)benzene (2.0 g, 3.30 mmol),tris(dibenzylideneacetone)dipalladium(0) (60.4 mg, 0.066 mmol), XPhosligand (80 mg, 0.163 mmol), and sodium tert-butoxide (444 mg, 4.62mmol). Each vial was fitted with a septa cap and evacuated andbackfilled with N₂. Dioxane (20 mL) was added to each vial and the vialswere placed on a ChemGlass reaction block and heated to 130° C. for 16h. After such time, the mixtures were cooled to rt, diluted with EtOAc,combined, and filtered over celite and concentrated. The residue waspurified via AFC. A brown solid was isolated (4.41 g, 79% yield).Following Part B (General Reaction Scheme I), gave the free phenol as ayellow solid (3.41 g, 79% yield).

Synthesis Example SE13: Phenol 192-(2H-benzotriazol-2-yl)-6-(p-tolylthio)-4-(2,4,4-trimethylpentan-2-yl)phenolbenzotriazole

Into a flame dried vial equipped with a stir bar was placed2-(2H-benzo[1,2,3]triazol-2-yl)-6-bromo-4-(2,4-dimethylpentan-2-yl)phenol(2.88 g, 6.92 mmol), tris(dibenzylideneacetone)dipalladium(0) (0.317 g,0.346 mmol), 1,1′bis(diphenylphospino)ferrocene (0.383 g, 0.692 mmol),potassium phosphate (1.76 g, 8.30 mmol), and 4-methylbenzenethioltoluene (1.031 g, 8.30 mmol). The vial was fitted with a septa cap andevacuated and backfilled with N₂. Toluene (14 mL) was added and thereaction was heated to 110° C. for 16 h. After such time, the mixtureswere cooled to rt, combined, diluted with EtOAc and filtered overcelite. The residue was purified via AFC. A beige solid was isolated(3.09 g, 97% yield). Following Part B (General Reaction Scheme I), gavethe free phenol as an ivory-colored solid (2.70 g, 90% yield).

Synthesis Example SE14: Phenol 202-(2H-benzotriazol-2-yl)-6-(p-tolylsulfinyl)-4-(2,4,4-trimethylpentan-2-yl)phenol

The following was adapted from a literature procedure (Org Lett. 2003,5, 235). Aryl sulfide from SE13 (1.2 g, 2.69 mmol) was added to a vialequipped with a stir bar. Ethanol (7 mL) and hydrogen peroxide (30%, 1.5mL) were added and N₂ was bubbled through the mixture for severalminutes. Scandium triflate (0.265 g, 0.539 mmol) was added and themixture allowed to stir rt overnight. After such time, the reaction wasquenched with H₂O (2 mL) and filtered. The filtrate was purified by AFCand a white solid was obtained (0.764 g, 61% yield). Another 0.167 g ofrecrystallized product from the mother liquor was obtained for a totalof 0.931 g (75% yield) of product.

Synthesis Example SE15: Phenol 212-(2H-benzotriazol-2-yl)-6-tosyl-4-(2,4,4-trimethylpentan-2-yl)phenol

Aryl sulfide from SE13 (1.5 g, 3.366 mmol) was dissolved indichloromethane (17 mL) in a vial equipped with a stir bar.M-Chloroperoxybenzoic acid, 50 wt % (2.56 g, 7.40 mmol) was added andthe reaction stirred until complete by TLC. The reaction was thenquenched with sat'd aqueous NaHCO₃ and the organic layer separated,dried (Na₂SO₄), filtered, and concentrated. It was purified by washingwith EtOAc and filtering. A white solid was obtained (1.34 g, 83%yield).

Synthesis Example SE16: Phenol 226,6′-thiobis(2-(2H-benzo[d][1,2,3]triazol-2-yl)-4-(2,4,4-trimethylpentan-2-yl)phenol)

6,6′-Thiobis(2-(2H-benzotriazol-2-yl)-4-(2,4,4-trimethylpentan-2-yl)phenol)from SE10 was oxidized using a literature procedure (Org Lett, 1999, 1,189).6,6′-Thiobis(2-(2H-benzotriazol-2-yl)-4-(2,4,4-trimethylpentan-2-yl)phenol)(7.39 mmol, 5.0 g) was dissolved in ethanol (5 mL) along with scandiumtriflate (0.74 mmol, 364 mg) and hydrogen peroxide.urea adduct (8.5mmol, 820 mg). The reaction stirred at 80° C. overnight and the whiteprecipitate was filtered and washed with water and ethanol. A 2:1mixture of the sulfoxide:sulfone was isolated (4.18 g, 81% yield).

Synthesis Example SE17: Phenol 236,6′-sulfonylbis(2-(2H-benzotriazol-2-yl)-4-(2,4,4-trimethylpentan-2-yl)phenol)

6,6′-Sulfonylbis(2-(2H-benzotriazol-2-yl)-4-(2,4,4-trimethylpentan-2-yl)phenol)was synthesized in a similar fashion as Example 24. Aryl sulfide fromSE10 (4.5 g, 6.6 mmol) was dissolved in dichloromethane (33 mL) in aflask equipped with a stir bar. m-Chloroperoxybenzoic acid, 50 wt %(7.40 mmol, 5.05 g) was added and the reaction stirred until complete byTLC. The reaction was then quenched with saturated aqueous NaHCO₃ andthe organic layer separated, dried (Na₂SO₄), filtered, and concentrated.It was purified by washing with EtOAc and filtering. A white solid wasobtained (2.9 g, 62% yield).

Synthesis Example SE18: Phenol 246,6′-(octadecylazanediyl)bis(2-(2H-benzotriazol-2-yl)-4-(2,4,4-trimethylpentan-2-yl)phenol)

Part A. The reaction product from part A of SE8, (4.0 g, 5.81 mmol) wasdissolved in dimethylformamide (60 mL) and to this, sodium hydride (6.40mmol, 256 mg) was added under a stream of N₂ at rt. The mixture wasstirred 10 min and then 1-iodooctadecane (6.40 mmol, 2.43 g) was addedand stirring continued for another 2 h. The reaction was quenched withsaturated aq ammonium chloride and extracted with EtOAc (3×). Thecombined organic layers were washed with water and then brine, driedwith Na₂SO₄, filtered and concentrated. No further purification wasperformed.

Part B. The product of Part A was dissolved in dichloromethane (40 mL)and cooled to a temperature of −78° C. while stirring under N₂. Borontribromide (12.20 mmol, 1.2 mL) was added dropwise and the reactionmixture allowed to slowly warm to rt. When the reaction was complete(analysis by TLC), water was added dropwise and the mixture was stirredfor 10 min. The organic layer was separated and the aqueous layerextracted with DCM (2×). The combined organic layers were washed withsaturated aqueous NaHCO₃ and brine, dried (Na₂SO₄ or MgSO₄), filteredand concentrated to give a viscous oil (5.16 g, 97% yield).

General Synthesis of Phenolate Salts

The above described phenols were used to prepare phenolate salts usingone of the synthetic routes described below. The reagents used toprepare the salts are shown in Tables A and B and the phenolate saltsformed are summarized in Table 1 below.

Synthetic Procedures

Alkoxide Route

Phenolic starting material is added to THF at 10-40% in a two-necked RBFequipped with a magnetic stir bar, condenser and addition funnel. Thesolution is stirred and heated to reflux until all of the phenolicstarting material is dissolved under nitrogen. A stoichometric amount ofmetal alkoxide stock solution is added dropwise from the addition funnelto the RBF under nitrogen. The solution is refluxed from 1 to 36 hours.The solution is stripped with reduced pressure, and the recovered powderis dried in under vacuum.

Hydride Route

Anhydrous methanol is added to a dry, three-necked RBF equipped with amagnetic stir bar, reflux condenser, nitrogen inlet, and a stopperedport. The metal hydride is added to the RBF and refluxed under nitrogenfor 30 minutes. The amount of hydride is used is added in 1-5%stoichiometric excess relative to the phenol being used, and the amountof phenol used is typically between 10-50% solids. After 30 minutes, thereaction is allowed to cool to room temperature and a stoichiometricamount of phenol is added the reaction by unstoppering the third portand adding the phenol in portions with a spatula.

The reaction mixture is restoppered and stirred under nitrogen for 24hours, at which point the reaction mixture is vacuum filtered and driedunder vacuum. We have also prepared hypostoichometric compounds whereless than the stoichiometric amount of cation is used andhyperstoichometric amounts where a stoichometric excess amount of cationis used.

Metal Route

The metal in its zero oxidation state was stirred with an alcohol in oneflask, while the phenol was stirred in an appropriate organic solvent ina separate flask. A typical solvent was toluene. The solutions arecombined into one flask once the metal was fully digested by thealcohol. The resulting precipitate was vacuum filtered, washed withmethanol, and dried under vacuum.

Alternative Routes

Other alternative routes can be envisioned for making these complexes.These routes could include reacting the phenols with an organometallic,such as butyl lithium.

Materials

The following is a table of commercially available materials andreagents that were used to prepare the phenolate salts

TABLE B Listing of reagents used to prepare phenolate salts MaterialSource Supplied Form CaH₂ MP Biomedicals Powder Mg(OCH₃)₂ Sigma-AldrichPowder Ca(OCH₃)₂ Sigma-Aldrich Powder Li(OCH₃) Sigma-Aldrich 2.2M inmethanol Na(OCH₂CH₃₎ Alfa-Aesar 21% w/v in ethanol K(OCH₃) Sigma-Aldrich25% in methanol Tetraethyl orthotitanate TCI America Liquid Co(II)Alfa-Aesar 5% w/v in (OCH₂CH₂OCH₃)₂ methoxyethanol Ca metal, granulesAlfa-Aesar Granules Methoxyethanol Alfa-Aesar Liquid

TABLE C Listing of phenols used in preparing phenolate salts PhenolTrade Name Source Phenol-1 TINUVIN P BASF Phenol-2 — Sigma-AldrichPhenol-3 — Synthesis Example SE3 Phenol-4 TINUVIN 327 BASF Phenol-5 —Synthesis Example SE2 Phenol-6 — Synthesis Example SE3 Phenol-7 —Synthesis Example SE4 Phenol-8 — Synthesis Example SE5 Phenol-9 —Synthesis Example SE6 Phenol-10 TINUVIN 234 BASF Phenol-11 — SynthesisExample SE7 Phenol-12 TINUVIN 360 BASF Phenol-13 — Synthesis Example SE8Phenol-14 — Synthesis Example SE9 Phenol-15 — Synthesis Example SE10Phenol-16 CGL 136 CIBA Phenol-17 — Synthesis Example SE11 Phenol-18 —Synthesis Example SE12 Phenol-19 — Synthesis Example SE13 Phenol-20 —Synthesis Example SE14 Phenol-21 — Synthesis Example SE15 Phenol-22 —Synthesis Example SE16 Phenol-23 — Synthesis Example SE17 Phenol-24 —Synthesis Example SE18

TABLE 1 Metal Salts Material Phenolate Cation Complex-1 Phenol-1 NaComplex-2 Phenol-1 K Complex-3 Phenol-2 Na Complex-4 Phenol-3 KComplex-5 Phenol-4 Na Complex-6 Phenol-5 Na Complex-7 Phenol-6 NaComplex-8 Phenol-7 Na Complex-9 Phenol-8 Na Complex-10 Phenol-9 NaComplex-11 Phenol-10 Na Complex-12 Phenol-10 K Complex-13 Phenol-11 NaComplex-14 Phenol-12 Li Complex-15 Phenol-12 Na Complex-16 Phenol-12 MgComplex-17^(a) Phenol-12 Ca Complex-18^(b) Phenol-12 Ca Complex-19Phenol-12 Co Complex-20^(c) Phenol-12 Ca Complex 21 Phenol-12 KComplex-22 Phenol-13 Ca Complex-23 Phenol-13 Na Complex-24 Phenol-14 CaComplex-25 Phenol-14 Na Complex-26 Phenol-15 Ca Complex-27 Phenol-15 NaComplex-28 Phenol-16 Na Complex-29 Phenol-17 Na Complex-30 Phenol-18 NaComplex-31 Phenol-19 Na Complex-32 Phenol-20 Na Complex-33 Phenol-21 NaComplex-34 Phenol-22 Ca Complex-35 Phenol-22 Na Complex-36 Phenol-23 CaComplex-37 Phenol-23 Na Complex-38^(c) Phenol-23 Ca Complex-39 Phenol-24Ca ^(a)Synthesized by the hydride route; ^(b)Synthesized by the alkoxideroute; ^(c)Synthesized by the metal route

Computational Data

As described above, an unexpected feature of these salt compounds isthat they form multi-metal centered complexes comprised of one, two,three, or more phenolates. We refer to these compounds as macromolecularsalt compositions. For simplicity, the macromolecular salt compositionsare referred to as monomers, dimers, trimers, etc, using the standardmacromolecular nomenclature. To demonstrate this feature, the heats ofreaction, ΔH_(r×n), were computed for several model compounds using thefollowing generalized reaction scheme:

The heats of reaction were calculated by first optimizing the structureswith the B3LYP density functional and MIDI! basis set followed by afrequency calculation to verify that the structure is a local minima.The geometry was further refined by optimizing with the B3LYP densityfunctional and 6-31G(d,p) basis set. The heats of reaction are computedfrom the B3LYP/6-31G(d,p) electronic energies. The reported heats ofreaction have been normalized to the number of metal centers. Allcomputations were run with NWChem 6.5 (M. Valiev, E. J. Bylaska, N.Govind, K. Kowalski, T. P. Straatsma, H. J. J. van Dam, D. Wang, J.Nieplocha, E. Apra, T. L. Windus, W. A. de Jong, “NWChem: acomprehensive and scalable open-source solution for large scalemolecular simulations” Comput. Phys. Commun. 181, 1477, 2010). Theresults are reported in Table 2.

TABLE 2 Computed heats of reaction in kcal/mol ΔH_(r×n) Model CompoundMetal Monomer Dimer Trimer Tetramer

Na K 23.6 23.1 47.6 43.2 51.3 48.5 51.5 47.4

Na 24.3 46.8 52.5 49.7

Na 25.0 54.9 58.2 55.5

Na K 31.9 33.0 55.4 51.1 45.3 45.8

Na Ca 36.3 15.9 47.7 56.6 51.3 59.2

Ca 19.0 53.1 56.7

NMR Data

Sample Prep:

The deuterated solvents used in this study were tetrahydrofuran (THF) orbenzene. The solvent was chosen based on the solubility of both theparent phenol and metal complex. Additionally, the solvents should notdisrupt the bonding by replacing a ligand in the complex. Theconcentration of the prepared samples was kept low such that the soluteconcentration has a negligible effect on the viscosity of the deuteratedsolvent selected. If the viscosity of the deuterated solvent was low(most organic solvents), the sample was prepared in a 3 mm NMR tuberather than the 5 mm NMR tube to eliminate convection in the tube.

Measurement and Data Processing:

The Diffusion measurements were carried out on either the Bruker 500 MHzor Bruker 600 MHz NMR spectrometers. The gradients were suitablycalibrated using a deuterated water sample. The standard Bruker 2D-DOSYsequence ledbpgp2s was used. For non-polymeric samples, the defaultsettings of Δ=75 ms and δ=3 ms are sufficient. If the size of thecomplex or aggregate is expected to have a radius >1 nm, then increasingΔ may be necessary. For a description of the DOSY pulse sequence, referto Antalek, B., Concepts in Magnetic Resonance, 14(4), 225-258 (2002).

The data was processed using Bruker Top Spin software. This is mostsuitable if there isn't spectral overlap between the compound ofinterest and residual monomer or another impurity in the sample.Selecting an exponential fit with a single component for each data pointworked very well. The diffusion coefficient of the water or the maindeuterated solvent can be used as internal controls from sample tosample to ensure there hasn't been a large viscosity change of thesolution compared to the neat deuterated solvent. The diffusioncoefficient of the analyte is measured in m²/s.

The diffusion spectra of the starting material and the phenolate complexcan be overlaid to easily visualize the difference in the diffusioncoefficients.

The proton spectra for many of the complexes are quite different fromthe starting material. The first difference was the disappearance of theOH proton observed in the starting material at about 12 ppm.

Also observed in the proton spectra is a splitting of many of theresonances. For example the 2 t-butyl groups on the iso-C8 groups are asingle resonance in the starting material with a peak at about 0.78 ppm.Upon reaction to form a metal complex, this resonance is often seen tosplit. In this example (Shown in FIG. 1) the resonance splits into 6distinct narrow peaks. This is the result of different t-butyl groups ondifferent molecules experience distinct magnetic environments. ExchangeNMR experiments were carried out, but no chemical exchange among themultiple t-butyl resonances in complex was observed using NOESYexperiments.

Aggregation numbers were calculated using an empirical relationship. Thediffusion coefficients are plotted versus the molecular weight on alog-log plot. According to several references, there should be a linearrelationship if the molecules have similar fractal exponents (Auge, S.et al.; J. Phys. Chem. B, 113, 1914-1918, (2009). Neufeld, R., Stalke,D.; Chem. Sci., DOI: 10.1039/c5sc00670h, (2015).).

The linear regression results in empirical formulas relating the Log ofthe molecular weight to the log of the diffusion coefficient in Benzene:Log M=−(1/0.73825)*(Log D+6.99798)And in THF:Log M=−(1/0.66235)*(Log D+7.11205)

These relationships are used to estimate the molecular weight of thephenolate complexes formed. The results are reported in Table 3.

TABLE 3 Diffusion coefficients and estimated size of complex. estimatedStructure Solvent log D size Phenol 1 THF −8.698 1 Complex 1 THF −8.9363 Complex 2 THF −8.978 3 Phenol 2 THF −8.743 1 Complex 3 THF −8.916 2Phenol 3 THF −8.764 1 Complex 4 THF −9.016 3 Phenol 4 THF −8.847 1Complex 5 THF −8.913 2 Phenol 5 Benzene −8.932 1 Complex 6 Benzene−9.194 2 Phenol 7 THF −8.88 1 Complex 8 THF −9.14 3 Phenol 8 THF −8.92 1Complex 9 THF −9.06 2 Phenol 9 THF −8.80 1 Complex 10 THF −9.18 2 Phenol10 Benzene −9.006 1 Complex 11 Benzene −9.101 2 Complex 12 Benzene−9.142 2 Phenol11 THF −8.948 1 Complex13 THF −9.075 2 Phenol 12 Benzene−9.098 1 Complex 14 Benzene −9.371 3 Complex 15 Benzene −9.293 2 Complex17 Benzene −9.390 3 Complex 18 Benzene −9.389 3 Complex 19 Benzene−9.425 3 Phenol 13 Benzene −9.087 1 Complex 23 Benzene −9.278 2 Complex22 Benzene −9.476 3 Phenol 14 Benzene −9.103 1 Complex 25 Benzene −9.2972 Phenol 15 Benzene −9.099 1 Complex 26 Benzene −9.357 2 Complex 27Benzene −9.269 2 Phenol 19 THF −8.880 1 Complex 31 THF −9.019 2 Phenol20 THF −8.898 1 Complex 32 THF −9.052 2 Phenol 21 THF −8.911 1 Complex33 THF −9.059 2 Phenol 22 Benzene −9.098 1 Complex 34 Benzene −9.340 2Complex 35 Benzene −9.378 2 Phenol 23 Benzene −9.106 1 Complex 37Benzene −9.288 2 Complex 38 Benzene −9.329 2 Complex 39 Benzene −9.319 2Phenol 24 Benzene −9.180 1 Complex 39 Benzene −9.367 2

Thermal Stability of Metal-Complexes

The thermal stability of the phenols and phenolates was measured bythermogravemetric analysis (TGA). The instrument used was the Q500 modelmade by TA Instruments. The procedure was to heat a dried sample at 10°C./min under Nitrogen to a temperature of 450° C. The startingtemperature was around 35° C. and a typical sample size was 5 mg. Thetemperatures for 5%, 10%, and 20% weight loss are reported in Table 4.In some cases it was necessary to drive off absorbed solvent or water inorder to report accurate weight losses. This was achieved by heating thesample to a temperature no greater than 180° C., cooling the sample backto room temperature, and then reheating to a temperature of 450° C.

TABLE 4 Temperatures in Celsius for 5, 10, and 20 percent weight loss asmeasured by TGA. 10% Weight 20% Weight Molecule 5% Weight Loss Loss LossPhenol-1 180 195 211 Complex 1 285 288 308 Complex 2 340 377 425 Phenol2 195 209 226 Complex 3 251 257 282 Phenol 3 95 195 212 Complex 4 240251 269 Phenol 4 208 222 238 Complex 5 386 403 442 Phenol 5 230 249 269Complex 6 376 387 397 Phenol 7 231 247 264 Complex 8 337 345 354 Phenol8 250 270 289 Complex 9 268 297 336 Phenol 9 264 283 302 Complex 10 418431 444 Phenol 10 264 280 295 Complex 12 258 290 328 Phenol 11 304 323343 Complex 13 319 350 394 Phenol 12 335 352 371 Complex 14 341 377 425Complex 15 321 360 414 Complex 17 325 359 399 Complex 19 257 300 322Complex 20 413 444 465 Phenol 13 348 373 394 Complex 22 384 407 432Complex 23 417 426 436 Phenol 14 321 350 377 Complex 24 333 371 403Complex 25 384 412 428 Phenol 15 243 291 353 Complex 26 414 424 441Complex 27 381 394 400 Phenol 16 260 275 293 Complex 28 265 283 299Phenol 17 247 261 278 Complex 29 334 346 356 Phenol 18 256 275 295Complex 30 267 304 331 Phenol 19 271 289 308 Complex 31 357 375 386Phenol 20 183 256 267 Complex 32 389 389 390 Phenol 21 264 305 329Complex 33 400 406 408 Phenol 22 242 263 294 Complex 34 387 409 440Complex 35 361 370 409 Phenol 23 210 330 361 Complex 36 356 394 421Complex 37 211 359 385 Complex 38 359 386 416 Phenol 24 296 343 365Complex 39 277 321 354Fluorescence Observations

Step A: Preparation of Samples

A spatula-tip of either phenol or metal complex was added with 2 mL ofTHF to a clean vial. The vial was sealed and the vial sat until thechemical completely dissolved.

Step B: Fluorescence Determination

The vials were and exposed to 365 nm wavelength UV light source in adarkened room and visual observations were recorded. The data are shownin Table 5 below.

TABLE 5 Fluorescence observations. Molecule Fluorescent Phenol 1 NoComplex 1 Strong Complex 2 Moderate-Strong Phenol 2 Weak Complex 3Moderate-Strong Phenol 4 No Complex 5 Moderate (red) Phenol 5 No Complex6 Strong Phenol 7 No Complex 8 Moderate-Strong Phenol 8 Weak Complex 9Moderate-Strong Phenol 9 No Complex 10 Strong Phenol 10 No Complex 11Moderate-Strong Complex 12 Moderate-Strong Phenol 11 Weak Complex 13Moderate-Strong Phenol 12 No Complex 14 Strong Complex 15Moderate-Strong Complex 16 Strong Complex 17 Moderate-Strong Complex 18Moderate-Strong Phenol 14 No Complex 24 Moderate-Strong Complex 25Moderate-Strong (orange) Phenol 15 No Complex 26 Strong (green) Complex27 Strong Phenol 16 No Complex 28 No Phenol 17 No Complex 29 WeakComplex 30 No Phenol 19 No Complex 31 Moderate-Strong (orange) Phenol 20No Complex 32 Strong (green) Phenol 21 Weak Complex 33 Strong (green)Phenol 22 No Complex 34 Strong (green) Complex 35 Strong Phenol 23 NoComplex 36 Strong (blue) Complex 37 Strong (blue) Complex 38 StrongPhenol 24 No Complex 39 Moderate-Strong (orange)

Anti-Oxidant Studies

Step A—Preparation of Compounded Additives

To prepare the samples, one of the additives was dry blended intopolypropylene. The concentration is specified in Table 6 below. Thematerials were compounded in a conical twin-screw extruder. Theextrusion temperature ranged from about 250° C. to 300° C. The extrusionspeeds ranged from 5 to 7 lbs/hr. The resins used were either MF-650X(PP-1) or MF-650W (PP-2), where both resins were purchased fromLyondellBasell.

Step B—Determination of Anti-Oxidant Ability

A modified oxidative-induction time (OIT) test that is similar to ASTMD3895 was performed. In the modified test, 2-6 mg of sample were placedin an aluminum pan and heated to 190° C. under nitrogen in adifferential scanning calorimeter (DSC). The atmosphere was thenswitched to an atmosphere of 21% oxygen and 78% nitrogen and thetemperature at between was held at 180° C. and 200° C. until an abruptincrease in evolved heat was displayed on the recorded thermogram. Theinduction time was then defined as the time between exposure to theoxygen-containing environment and onset of heat evolution. The datapresented in Table 6 are an average of 3 samples.

TABLE 6 OIT data for metal complexes. Additive Temperature OIT ResinAdditive Concentration (° C.) (min) PP-1 180 45.0 PP-2 180 26.5 PP-1 19018.1 PP-1 200 6.5 PP-1 Phenol 11 0.2% 200 291.1 PP-1 Complex 13 0.2% 200342.7 PP-1 Complex 9 190 32.8 PP-2 Phenol 12 0.2% 180 27.7 PP-1 Complex21 180 53.4 PP-2 Complex 17 180 81.6 PP-2 Complex 17 180 107.7 PP-1Complex 24 0.6% 190 151.2 PP-1 Phenol 13 0.2% 190 29.9 PP-1 Complex 220.2% 190 187.6 PP-1 Phenol 14 0.2% 190 5.05 PP-1 Complex 24 0.2% 19062.7

What is claimed is:
 1. An antioxidant composition comprising one or moremacromolecular salt compositions, the macromolecular salt compositioncomprising an assembly of metal salts comprising repeat units of asubstituted benzotriazole phenolate anion and a metal cation with thestructure:

wherein each R², R³, R⁴, R⁵, R⁶, R⁷, and R⁸, independently comprises ahydrogen atom, an alkyl group, an alkenyl group, an aryl group, ahalogen atom, or a substituted heteroatom group comprising a—B(OR¹⁸)(OR¹⁹), a —SiR²⁰ ₃, a —CH₂—R⁹, an —O—R⁹, a —N—R⁹R¹⁰, a —S—R⁹, a—S(O)—R⁹, or a —S(O)₂—R⁹ group, wherein R⁹ comprises a hydrogen atom, analkyl group, an alkenyl group, an aryl group, or a heteroatom-containinggroup comprising one or more oxygen, nitrogen, sulfur, or phosphorousatoms, wherein the —B(OR¹⁸)(OR¹⁹), —SiR²⁰ ₃, —CH₂—R⁹, —O—R⁹, —N—R⁹R¹⁰,—S—R⁹, —S(O)—R⁹, or —S(O)₂—R⁹ group may be neutral or anionic, and R¹⁰comprises a hydrogen atom, an alkyl group, an alkenyl group, an arylgroup, or a heteroatom-containing group comprising one or more oxygen,nitrogen, sulfur, or phosphorous atoms, or R⁹ and R¹⁰ together with theatoms connecting form a heterocyclic ring structure, R¹⁸ and R¹⁹ areindependently hydrogen atoms, alkyl groups or R¹⁸ and R¹⁹ together withthe atoms connecting form a heterocyclic ring structure, each R²⁰independently comprises an alkyl group; R¹ is a hydrogen atom, asubstituted alkyl group, an alkenyl group, an aryl group, a halogenatom, or a substituted heteroatom group comprising a —B(OR⁸)(OR¹⁹), a—SiR²⁰ ₃, a —CH₂—R⁹, an —O—R⁹, a —N—R⁹R¹⁰, a —S—R⁹, a —S(O)—R⁹, or a—S(O)₂—R⁹ group, and wherein when R¹ is hydrogen, R³ is an alkyl groupcomprising 4 carbon atoms, or an alkoxy group; n=1; and M comprises ametal atom with a valency of n; and the macromolecular assemblycomprises 2-4 repeat units.
 2. The antioxidant composition of claim 1,wherein M comprises lithium, sodium, or potassium.
 3. The antioxidantcomposition of claim 1, wherein R¹ comprises an —O—R⁹ group wherein R⁹comprises: an alkyl group with 1-20 carbon atoms; or an aryl group; andR³ is an alkyl group with 1-20 carbon atoms.
 4. The antioxidantcomposition of claim 3, wherein R⁹ comprises: an alkyl group with 1-6carbon atoms; or an aryl group comprising a 3-methyl phenyl group, or a4-methyl phenyl group.
 5. The antioxidant composition of claim 1,wherein R¹ comprises an —N—R⁹R¹⁰ group wherein R⁹ comprises: an alkylgroup with 1-20 carbon atoms; or an aryl group; R¹⁰ comprises a hydrogenatom or alkyl group with 1-6 carbon atoms; and R³ is an alkyl group with1-20 carbon atoms.
 6. The antioxidant composition of claim 5, wherein R⁹comprises: an alkyl group with 1-6 carbon atoms; or an aryl groupcomprising a 4-alkyl substituted phenyl group, wherein the alkylsubstituted group has 1-6 carbon atoms; R¹⁰ comprises a hydrogen atom.7. The antioxidant composition of claim 1, wherein R¹ comprises, asubstituted alkyl, alkylene, or an aryl group; and R³ is an alkyl groupwith 1-20 carbon atoms, or an alkoxy group with 1-6 carbon atoms.
 8. Theantioxidant composition of claim 1, wherein R¹ comprises a halogen atomor a —SiR²⁰ ₃ group wherein each R²⁰ comprises an alkyl group with 1-4carbon atoms; and R³ is an alkyl group with 1-20 carbon atoms.
 9. Theantioxidant composition of claim 1, wherein the antioxidant compositioncomprises a mixture of macromolecular salts.
 10. A macromolecular saltcomposition comprising an assembly of metal salts comprising repeatunits of a substituted benzotriazole phenolate anion and a metal cationwith the structure:

wherein each R², R³, R⁴, R⁵, R⁶, R⁷, and R⁸, independently comprises ahydrogen atom, an alkyl group, an alkenyl group, an aryl group, ahalogen atom, or a substituted heteroatom group comprising a—B(OR⁸)(OR¹⁹), a —SiR²⁰ ₃, a —CH₂—R⁹, an —O—R⁹, a —N—R⁹R¹⁰, a —S—R⁹, a—S(O)—R⁹, or a —S(O)₂—R⁹ group, wherein R⁹ comprises a hydrogen atom, analkyl group, an alkenyl group, an aryl group, or a heteroatom-containinggroup comprising one or more oxygen, nitrogen, sulfur, or phosphorousatoms, wherein the —B(OR¹⁸)(OR¹⁹), —SiR²⁰ ₃, —CH₂—R⁹, —O—R⁹, —N—R⁹R¹⁰,—S—R⁹, —S(O)—R⁹, or —S(O)₂—R⁹ group may be neutral or anionic, and R¹⁰comprises a hydrogen atom, an alkyl group, an alkenyl group, an arylgroup, or a heteroatom-containing group comprising one or more oxygen,nitrogen, sulfur, or phosphorous atoms, or R⁹ and R¹⁰ together with theatoms connecting form a heterocyclic ring structure, R¹⁸ is and R¹⁹ areindependently hydrogen atoms, alkyl groups or R¹⁸ is and R¹⁹ togetherwith the atoms connecting form a heterocyclic ring structure, each R²⁰independently comprises an alkyl group; R¹ is a hydrogen atom, asubstituted alkyl group, an alkenyl group, an aryl group, a halogenatom, or a substituted heteroatom group comprising a —B(OR¹⁸)(OR¹⁹), a—SiR²⁰ ₃, a —CH₂—R⁹, an —O—R⁹, a —N—R⁹R¹⁰, a —S—R⁹, a —S(O)—R⁹, or a—S(O)₂—R⁹ group, and wherein when R¹ is hydrogen, R³ is an alkyl groupcomprising 4 carbon atoms, or an alkoxy group; n=1; and M comprises ametal atom with a valency of n; and the macromolecular assemblycomprises 2-4 repeat units.
 11. The salt composition of claim 10,wherein M comprises lithium, sodium, or potassium.
 12. The saltcomposition of claim 10, wherein R¹ comprises an —O—R⁹ group wherein R⁹comprises: an alkyl group with 1-6 carbon atoms; or an aryl groupcomprising a 3-methyl phenyl group, or a 4-methyl phenyl group; and R³is an alkyl group with 1-20 carbon atoms.
 13. The salt composition ofclaim 10, wherein R¹ comprises an —N—R⁹R¹⁰ group wherein R⁹ comprises:an alkyl group with 1-6 carbon atoms; or an aryl group comprising a4-alkyl substituted phenyl group, wherein the alkyl substituted grouphas 1-6 carbon atoms; R¹⁰ comprises a hydrogen atom or alkyl group with1-6 carbon atoms; and R³ is an alkyl group with 1-20 carbon atoms. 14.The salt composition of claim 10, wherein R¹ comprises a substitutedalkyl, alkylene, or an aryl group; and R³ is an alkyl group with 1-20carbon atoms, or an alkoxy group with 1-6 carbon atoms.
 15. The saltcomposition of claim 10, wherein R¹ comprises a halogen atom or a —SiR²⁰₃ group wherein each R²⁰ comprises an alkyl group with 1-4 carbon atoms;and R³ is an alkyl group with 1-20 carbon atoms.